Heteroacene compounds for organic electronics

ABSTRACT

The present invention provides compounds of formula (1) wherein o is 1, 2 or 3, p is 0, 1 or 2, n is 0, 1 or 2, m is 0, 1 or 2, and A is a mono- or polycyclic ring system, which may contain at least one heteroatom, and an electronic device comprising the compounds as semiconducting material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/IB2013/060391, filed Nov. 25. 2013, which claims benefit ofEuropean Application No. 12195227.9, filed Dec. 3, 2012, both of whichare incorporated herein by reference in their entirety.

Organic semiconducting materials can be used in electronic devices suchas organic photovoltaic devices (OPVs), organic field-effect transistors(OFETs), organic light emitting diodes (OLEDs), and organicelectrochromic devices (ECDs).

For efficient and long lasting performance, it is desirable that theorganic semiconducting material-based devices show high charge carriermobility as well as high stability, in particular towards oxidation byair.

Furthermore, it is desirable that the organic semiconducting materialsare compatible with liquid processing techniques such as spin coating asliquid processing techniques are convenient from the point ofprocessability, and thus allow the production of low cost organicsemiconducting material-based electronic devices. In addition, liquidprocessing techniques are also compatible with plastic substrates, andthus allow the production of light weight and mechanically flexibleorganic semiconducting material-based electronic devices.

The organic semiconducting materials can be either p-type or n-typeorganic semiconducting materials. It is desirable that both types oforganic semiconducting materials are available for the production ofelectronic devices.

The use of heteroacene compounds containing thieno units as p-typesemiconducting materials in electronic devices is known in the art.

WO 2011/067192 describes copolymers of the general formula

and in particular the copolymer of formula

An organic field effect transistor (OFET) containing this particularcopolymer as semiconducting material shows a charge carrier mobility of1.29 (±0.28)*10⁻³ cm²/V s and an on-off ratio of 3.8 (±0.2)*10³.

Wang, J.; Y; Zhou, Y.; Yan, J.; Ding, L.; Ma, Y.; Cao, Y.; Wang, J.;Pei, J. Chem. Mater. 2009, 21, 2595 to 2597 describes the followingcompounds

An organic field effect transistor (OFET) containing one of thesecompounds as p-type semiconducting material shows a charge carriermobility up to 0.4 cm²/V s.

US 2008/142792 describes compounds of general formula

An organic field effect transistor (OFET) containing the followingcompound

shows a charge carrier mobility of 0.08 cm²/V s.

Yamamoto, T.; Takimiya, K. J. Am. Chem. Soc. 2007, 129, 2224 to 2225describe

An organic field effect transistor (OFET) containing DNTT shows a chargecarrier mobility of higher than 2.0 cm²/V s and an on-off ratio of >10⁷.

Nakayama, K.; Hirose, Y.; Soeda, J.; Yoshizumi, M.; Uemura, T.; Uno, M.;Li, W.; Kang, M. J.; Yamagishi, M.; Okada, Y.; Miyazaki, E.; Y.Nakazawa, Y.; Nakao, A.; Takimiya, K.; Takeya, J. Adv. Mater. 2011, 23,1626 to 1629 describes the preparation of organic field effecttransistor (OFET) containing C₁₀-DNTT having the following formula

The deposition of C₁₀-DNTT was performed from an approximately 100° C.hot solution of C₁₀-DNTT in 1,2-dichlorobenzene. The organic fieldeffect transistors (OFET) containing C₁₀-DNTT show charge carriermobilities exceeding 10.0 cm²/V s.

Niimi, K.; Shinamura, S.; Osaka, I.; Miyazaki, E.; Takimiya, K. J. Am.Chem Soc. 2011, 133, 8732 to 8739 describes the following compound

A charge carrier mobility as high as 3.0 cm²/V s was achieved withvapor-processed DATT-based devices.

US 2011/0210319 describes organic field effect transistor (OFET)containing the following π-extended S-containing heteroarene compounds

These OFETs show the following charge carrier mobilities: 1.2 (compound167), 1.8 (compound 250), 2.0 (compound 638), 1.7 (compound 881) cm²/Vs, and the following on-off ratios: 2*10⁶ (compound 167), 3*10⁶(compound 250), 4*10⁵ (compound 638) and 3*10⁶ (compound 881).

WO 2013/039842 describes compounds of the following formula

It was the object of the present invention to provide improved organic,preferably p-type, semiconducting materials.

This object is solved by the compounds of embodiment 1, the electronicdevice of embodiment 13 and the use of embodiment 15.

The organic semiconducting materials of the present invention arecompounds of formula

wherein

o is 1, 2 or 3,

p is 0, 1 or 2,

n is 0, 1 or 2,

m is 0, 1 or 2,

A is a mono- or polycyclic ring system, which may contain at least oneheteroatom,

R¹⁰ is at each occurrence selected from the group consisting of halogen,—CN, —NO₂, C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, C₄₋₈-cycloalkyl,C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and        C₂₋₃₀-alkynyl, but not adjacent CH₂-groups, may be replaced with        —O— or —S—,    -   C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and C₂₋₃₀-alkynyl may be optionally        substituted with 1 to 10 R¹⁰⁰ residues at each occurrence        selected from the group consisting of halogen, —CN, —NO₂, —OH,        —NH₂, —NH(R^(a)), —N(R^(a))₂, —NH—C(O)—(R^(a)),        —N(R^(a))—C(O)—(R^(a)), —N[C(O)—(R^(a))]₂, —C(O)—R^(a),        —C(O)—OR^(a), —C(O)NH₂, —CO(O)NH—R^(a), —C(O)N(R^(a))₂,        —O—R^(a), —O—C(O)—R^(a), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to        14 membered heterocyclic ring system, and    -   wherein        -   R^(a) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic        ring system may be substituted with 1 to 5 residues at each        occurrence selected from the group consisting of halogen, CN,        —NO₂, —OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl and C₂₋₁₀-alkynyl,        and

R³ and R¹¹ are independently from each other at each occurrence selectedfrom the group consisting of halogen, —CN, —NO₂, C₁₋₃₀-alkyl,C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and        C₂₋₃₀-alkynyl, but not adjacent CH₂-groups, may be replaced with        —O— or —S—, and    -   C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and C₂₋₃₀-alkynyl may be optionally        substituted with 1 to 10 R¹⁰¹ residues independently selected        from the group consisting of halogen, —CN, —NO₂, —OH, —NH₂,        —NH(R^(b)), —N(R^(b))₂, —NH—C(O)—(R^(b)),        —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂, —C(O)—R^(b),        —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b), —C(O)N(R^(b))₂,        —O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to        14 membered heterocyclic ring system, and wherein    -   wherein        -   R^(b) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl or C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic        ring system may be substituted with 1 to 5 residues        independently selected from the group consisting of halogen, CN,        —NO₂, —OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.

Examples of monocyclic ring systems A are

wherein R¹⁰⁰ is H or C₁₋₁₀-alkyl.

Examples of polycyclic ring systems A are

wherein R¹⁰¹ is H or C₁₋₁₀-alkyl.

C₁₋₁₀-alkyl, C₁₋₂₀-alkyl and C₁₋₃₀-alkyl can be branched or unbranched.Examples of C₁₋₁₀-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl,n-(1-ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyland n-decyl. Examples of C₁₋₂₀-alkyl are C₁₋₁₀-alkyl and n-undecyl,n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀).Examples of C₁₋₃₀-alkyl are C₁₋₂₀-alkyl and n-docosyl (C₂₂),n-tetracosyl (C₂₄), n-hexacosyl (C₂₆), n-octacosyl (C₂₈) andn-triacontyl (C₃₀). Examples of C₈₋₂₀-alkyl are n-octyl,n-(2-ethyl)-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl,n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C₂₀)

C₂₋₁₀-alkenyl, C₂₋₂₀-alkenyl and C₂₋₃₀-alkenyl can be branched orunbranched. Examples of C₁₋₂₀-alkenyl are vinyl, propenyl,cis-2-butenyl, trans-2-butenyl, 3-butenyl, cis-2-pentenyl,trans-2-pentenyl, cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl,2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl.Examples of C₂₋₂₀-alkenyl are C₂₋₁₀-alkenyl and linoleyl (C₁₈),linolenyl (C₁₈), oleyl (C₁₈), and arachidonyl (C₂₀). Examples ofC₂₋₃₀-alkenyl are C₂₋₂₀-alkenyl and erucyl (C₂₂).

C₂₋₁₀-alkynyl, C₂₋₂₀-alkynyl and C₂₋₃₀-alkenyl can be branched orunbranched. Examples of C₂₋₁₀-alkynyl are ethynyl, 2-propynyl,2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl anddecynyl. Examples of C₂₋₂₀-alkynyl and C₂₋₃₀-alkenyl are undecynyl,dodecynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl,hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C₂₀).

Examples of C₄₋₈-cycloalkyl are cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl.

Examples of C₆₋₁₄-aryl are phenyl and naphthyl.

The 5 to 14 membered heterocyclic ring systems can be monocyclic orpolycyclic.

Examples of 5 to 14 membered heterocyclic ring systems are pyrrolidinyl,1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl,2,3-dihydrofuryl, tetrahydrothiophenyl, 2,3-dihydrothiophenyl,imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl,oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl,isothiazolidinyl, isothiazolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl,1,4,2-dithiazolyl, piperidyl, piperidino, tetrahydropyranyl, pyranyl,thianyl, thiopyranyl, piperazinyl, morpholinyl and morpholino,thiazinyl, azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl,thiepinyl, 1,2-diazepinyl, 1,3-thiazepinyl, decahydronaphthyl, pyrrolyl,furyl, thiophenyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxadiazolyl,tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl,1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, azepinyl and1,2-diazepinyl.

Examples of halogen are F, Cl, Br and I.

Preferably, o is 1 or 2. More preferably, o is 1.

Preferably, p, n and m are 0 or 1. More preferably, p, n and m are 0.

Preferably, A is a mono- or dicyclic ring system A, which contains atleast one heteroatom.

More preferably, A is a mono- or dicyclic ring system A, which containsat least one S atom.

Most preferably, A is a monocyclic ring system A, which contains atleast one S atom.

In particular A is

Preferably, R¹⁰ is at each occurrence selected from the group consistingof C₁₋₃₀-alkyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 memberedheterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—,    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰⁰        residues at each occurrence selected from the group consisting        of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(a)), —N(R^(a))₂,        —NH—C(O)—(R^(a)), —N(R^(a))—C(O)—(R^(a)), —N[C(O)—(R^(a))]₂,        —C(O)—R^(a), —C(O)—OR^(a), —C(O)NH₂, —CO(O)NH—R^(a),        —C(O)N(R^(a))₂, —O—R^(a), —O—C(O)—R^(a), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and    -   wherein        -   R^(a) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and

C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ringsystem may be substituted with 1 to 5 residues at each occurrenceselected from the group consisting of halogen, CN, —NO₂, —OH, —NH₂,C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl and C₂₋₁₀-alkynyl.

More preferably, R¹⁰ is at each occurrence C₁₋₃₀-alkyl, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—,    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰⁰        residues at each occurrence selected from the group consisting        of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(a)), —N(R^(a))₂,        —NH—C(O)—(R^(a)), —N(R^(a))—C(O)—(R^(a)), —N[C(O)—(R^(a))]₂,        —C(O)—R^(a), —C(O)—OR^(a), —C(O)NH₂, —CO(O)NH—R^(a),        —C(O)N(R^(a))₂, —O—R^(a), —O—C(O)—R^(a), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and    -   wherein        -   R^(a) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system.

Even more preferably, R¹⁰ is at each occurrence C₁₋₃₀-alkyl.

Most preferably, R¹⁰ is at each occurrence C₈₋₂₀-alkyl.

In particular, R¹⁰ is at each occurrence C₁₄H₂₉.

Preferably, R³ and R¹¹ are independently from each other at eachoccurrence selected from the group consisting of halogen, —CN,C₁₋₃₀-alkyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 memberedheterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—, and    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰¹        residues independently selected from the group consisting of        halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,        —NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,        —C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b),        —C(O)N(R^(b))₂, —O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and        wherein    -   wherein        -   R^(b) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl or C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic        ring system may be substituted with 1 to 5 residues        independently selected from the group consisting of halogen, CN,        —NO₂, —OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.

More preferably, R³ and R¹¹ are independently from each other at eachoccurrence selected from the group consisting of C₁₋₃₀-alkyl,C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—, and    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰¹        residues independently selected from the group consisting of        halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,        —NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,        —C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b),        —C(O)N(R^(b))₂, —O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and        wherein    -   wherein        -   R^(b) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl or C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system may        be substituted with 1 to 5 residues independently selected from        the group consisting of halogen, CN, —NO₂, —OH, —NH₂,        C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.

Even more preferably, R³ and R¹¹ are independently from each other ateach occurrence C₁₋₃₀-alkyl.

Preferred are compounds of formula

wherein

o is 1, 2 or 3,

p is 0, 1 or 2,

n is 0, 1 or 2,

m is 0, 1 or 2,

A is a mono- or dicyclic ring system, which contains at least oneheteroatom,

R¹⁰ is at each occurrence C₁₋₃₀-alkyl, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—,    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰⁰        residues at each occurrence selected from the group consisting        of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(a)), —N(R^(a))₂,        —NH—C(O)—(R^(a)), —N(R^(a))—C(O)—(R^(a)), —N[C(O)—(R^(a))]₂,        —C(O)—R^(a), —C(O)—OR^(a), —C(O)NH₂, —CO(O)NH—R^(a),        —C(O)N(R^(a))₂, —O—R^(a), —O—C(O)—R^(a), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and    -   wherein        -   R^(a) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl and C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and

R³ and R¹¹ are independently from each other at each occurrence selectedfrom the group consisting of halogen, —CN, C₁₋₃₀-alkyl, C₄₋₈-cycloalkyl,C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—, and    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰¹        residues independently selected from the group consisting of        halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,        —NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,        —C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b),        —C(O)N(R^(b))₂, —O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and        wherein    -   wherein        -   R^(b) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl or C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic        ring system may be substituted with 1 to 5 residues        independently selected from the group consisting of halogen, CN,        —NO₂, —OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.

More preferred are compounds of formula

wherein

o is 1 or 2,

p is 0 or 1,

n is 0 or 1,

m is 0 or 1,

A is a mono- or dicyclic ring system A, which contains at least S atom,

R¹⁰ is at each occurrence C₁₋₃₀-alkyl, and

R³ and R¹¹ are independently from each other at each occurrence selectedfrom the group consisting of C₁₋₃₀-alkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein

-   -   at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacent        CH₂-groups, may be replaced with —O— or —S—, and    -   C₁₋₃₀-alkyl may be optionally substituted with 1 to 10 R¹⁰¹        residues independently selected from the group consisting of        halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,        —NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,        —C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b),        —C(O)N(R^(b))₂, —O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl,        C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, and        wherein    -   wherein        -   R^(b) is at each occurrence selected from the group            consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,            C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered            heterocyclic ring system, wherein            -   C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl or C₂₋₂₀-alkynyl may be                substituted with 1 to 5 residues at each occurrence                selected from the group consisting of halogen, CN, —NO₂,                —OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14                membered heterocyclic ring system, and    -   C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system may        be substituted with 1 to 5 residues independently selected from        the group consisting of halogen, CN, —NO₂, —OH, —NH₂,        C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.

Most preferred are compounds of formula

wherein

o is 1 or 2,

p is 0 or 1,

n is 0 or 1,

m is 0 or 1,

A is

R¹⁰ is at each occurrence C₈₋₂₀-alkyl, and

R³ and R¹¹ are independently from each other at each occurrenceC₁₋₃₀-alkyl.

In particular preferred compounds of formula (1) are the compounds offormulae

wherein R¹⁰ is C₈₋₂₀-alkyl.

Even more particular preferred compounds of formula (1) are thecompounds of formulae

The compounds of formula (1) can be prepared by methods known in theart.

For example, the compound of formula (1a) can be prepared as outlinedbelow:

The compound of formula (1a) can be prepared by treating a compound offormula (2a) with a suitable catalyst such as PtCl₂, usually at elevatedtemperatures such as at between 50° C. and 120° C., and in the presenceof an inert solvent such as toluene.

The compound of formula (2a) can be prepared by treating a compound offormula (3a) with K₂CO₃ in a suitable solvent such asmethanol/tetrahydrofuran, usually at ambient temperatures such asbetween 18° C. and 30° C.

The compound of formula (3a) can be prepared by treating a compound offormula (4a) with trimethyl(2-tributylstannylethynyl)silane and asuitable catalyst such as Pd(PPh₃)₄, usually at elevated temperaturessuch as between 60° C. and 180° C., usually in the presence of asuitable solvent such as dimethylformamide.

The compound of formula (4a) can be prepared by treating compound offormula (5a) with a halogen-donating agent, especially abromine-donating agent such as Br₂ or N-bromo-succinimide, usually attemperatures between −5° C. and 30° C., and usually in the presence ofan inert solvent such as chloroform.

The compound of formula (5a) can be prepared by reacting a compound offormula (8a) with a compound of formula (6a) in the presence of asuitable solvent such as Pd(PPh₃)₄, usually at elevated temperaturessuch as between 50° C. and 180° C., and usually in the presence of asuitable solvent such as dimethylformamide.

The compound of formula (6a) can be prepared by adding a compound offormula (7a) to a solution of lithiumdimethylamide in tetrahydrofuran.

The compound of formula (8a) can be prepared by treatingthieno[3,2-b]thiophene first with n-butyllithium at −78° C. intetrahydrofuran, and then with trimethyltin chloride at −78° C. intetrahydrofurane.

For example, the compound of formula (1b) can be prepared as outlinedbelow:

The compound of formula (1b) can be prepared by treating a compound offormula (9a) with methanesulfonic acid, usually in an inert solvent suchdichloromethane, and usually at temperatures between −5° C. and 30° C.

The compound of formula (9a) can be prepared by adding a compound offormula (10a) to a solution obtained by treating a solution of(methoxymethyl)triphenylphosphonium chloride in tetrahydrofurane withpotassium tert-butoxide. The reaction is usually performed at atemperature in the range of from −5° C. to 30° C.

The compound of formula (10a) can be prepared by treating a compound offormula (11a) first with butyllithium in tetrahydrofurane at −78° C.,followed by treatment with dimethylformamide.

The compound of formula (11a) can be prepared by reacting a compound offormula (8a) with a compound of formula (12a) in the presence of asuitable catalyst such as Pd(PPh₃)₄, and in the presence of a suitablesolvent such as dimethylformamide.

The compound of formula (12a) can be prepared by first adding a compoundof formula (7a) to a solution of lithiumdimethylamide in tetrahydrofuranat −78° C., and then by adding the so-obtained solution to a solution ofiodine in tetrahydrofurane at −78° C.

Also part of the present invention is an electronic device comprisingthe compound of formula (1). Preferably, the electronic device is anorganic field effect transistor (OFET).

Usually, an organic field effect transistor comprises a dielectriclayer, a semiconducting layer and a substrate. In addition, an organicfield effect transistor usually comprises a gate electrode andsource/drain electrodes.

Preferably, the compound of formula (1) is present in the semiconductinglayer. The semiconducting layer can have a thickness of 5 to 500 nm,preferably of 10 to 100 nm, more preferably of 20 to 50 nm.

The dielectric layer comprises a dielectric material. The dielectricmaterial can be silicon dioxide, or, an organic polymer such aspolystyrene (PS), poly(methylmethacrylate) (PMMA), poly(4-vinylphenol)(PVP), poly(vinyl alcohol) (PVA), benzocyclobutene (BCB), or polyimide(PI). The dielectric layer can have a thickness of 10 to 2000 nm,preferably of 50 to 1000 nm, more preferably of 100 to 800 nm.

The source/drain electrodes can be made from any suitable source/drainmaterial, for example gold (Au) or tantalum (Ta). The source/drainelectrodes can have a thickness of 1 to 100 nm, preferably from 20 to 70nm.

The gate electrode can be made from any suitable gate material such ashighly doped silicon, aluminium (Al), tungsten (W), indium tin oxide,gold (Au) and/or tantalum (Ta). The gate electrode can have a thicknessof 1 to 200 nm, preferably from 5 to 100 nm.

The substrate can be any suitable substrate such as glass, or a plasticsubstrate such as polyethersulfone, polycarbonate, polysulfone,polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).Depending on the design of the organic field effect transistor, acombination of the gate electrode and the dielectric layer can alsofunction as substrate.

The organic field effect transistor can be prepared by methods known inthe art.

For example, a bottom-gate top-contact organic field effect transistorcan be prepared as follows: The gate electrode can be formed bydepositing the gate material, for example highly doped silicon, on oneside of the dielectric layer made of a suitable dielectric material, forexample silicium dioxide. The semiconducting layer can be formed byeither solution deposition or thermal evaporation in vacuo of a compoundof formula (1) on the other side of the dielectric layer. Source/drainelectrodes can be formed by deposition of a suitable source/drainmaterial, for example tantalum (Ta) and/or gold (Au), on thesemiconducting layer through a shadow masks. The channel width (W) istypically 50 μm and the channel length (L) is typically 1000 μm.

Also part of the invention is the use of the compound of formula (1) assemiconducting material.

The compounds of formula (1) show a high charge carrier mobility and ahigh stability, in particular towards oxidation, under ambientconditions. Furthermore the compounds of formula (1) are compatible withliquid processing techniques.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the design of the bottom-gate, top-contact organic fieldeffect transistor of example 3.

FIG. 2 shows the drain current I_(d) [A] in relation to the gate-sourcevoltage V_(g) [V] (top transfer curve) and the drain current I_(d)^(1/2) [A^(1/2)] in relation to the gate-source voltage V_(g) [V](bottom transfer curve) for the bottom-gate top-contact organic fieldeffect transistor of example 3 comprising compound 1b as semiconductingmaterial at a drain voltage V_(d) of −60 V.

FIG. 3 shows the drain current I_(d) [A] in relation to the drainvoltage V_(d) [V] (output curves) for the bottom-gate, top-contactorganic field effect transistor of example 3 comprising compound 1b assemiconducting material at a gate-source voltage V_(g) of −60 V (firstand top curve), −40 V (second curve), −20 V (third curve) and 0 V(fourth and bottom curve).

FIG. 4 shows the drain current I_(d) [A] in relation to the gate-sourcevoltage V_(g) [V] (top transfer curve) and the drain current I_(d)^(1/2) [10⁻³ A^(1/2)] in relation to the gate-source voltage V_(g) [V](bottom transfer curve) for the bottom-gate top-contact organic fieldeffect transistor of example 3 comprising compound 1a as semiconductingmaterial at a drain voltage V_(d) of −40 V.

FIG. 5 shows the drain current I_(d) [A] in relation to the drainvoltage V_(d) [V] (output curves) for the bottom-gate, top-contactorganic field effect transistor of example 3 comprising compound 1a assemiconducting material at a gate-source voltage V_(g) of −60 V (firstand top curve), −55 V (second curve), −50 V (third curve) and −45 V(fourth and bottom curve).

EXAMPLES Example 1

Preparation of Compound 1a

Preparation of Compound 8a

Commercially available thieno[3,2-b]thiophene (4 g, 32 mmol) in THF (100mL) was cooled to −78° C. and n-butyllithium solution (1.6 M, 42 mL, 66mmol) was added drop wise over 60 minutes using a dropping funnel. Thereaction mixture was gradually warmed to room temperature and stirredfor 3 hrs. The resultant suspension was again cooled to −78° C. and asolution of trimethyltin chloride (13.15 g, 66 mmol) in THF (50 mL) wasadded drop wise over 30 minutes using a dropping funnel. The resultantmixture was gradually warmed to room temperature and stirred for 16 hrs.The reaction mixture was quenched with water (150 mL) and extracted withEt₂O (2×100 mL). Combined organic layers were washed with brine andconcentrated to give brown solids, which were triturated with ethanol(4×20 mL). The solids were collected by filtration and washed thoroughlywith ethanol (2×20 mL) to yield compound 8a as a white solid (10 g,68%), which was used directly in the next step without furtherpurification.

¹H NMR (400 MHz, CDCl₃) δ 7.26 (s, 2H), 0.37 (s, 18H).

Preparation of Compound 6a

Commercially available LDA solution (2 M, 24 mL, 47 mmol) was diluted inTHF (65 mL) solution at 0° C. A solution of2-bromo-5-tetradodecyl-thiophene (7a) (14 g, 39 mmol) in THF (65 mL) wasadded drop wise to the dilute LDA solution at 0° C. over 1 h using adropping funnel. The resultant mixture was gradually warmed to roomtemperature and stirred for 3 hrs. The reaction mixture was quenchedwith water (150 mL) and extracted with Et₂O (2×100 mL). The combinedorganic layers were washed with brine and concentrated to give a brownoil, which was purified by column chromatography on silica gel using100% hexane to yield compound 6a as yellow oil (12.5 g, 89%). ¹H NMR(400 MHz, CDCl₃) δ 6.99 (s, 1H), 6.70 (s, 1H), 2.77 (t, 2H, J=8 Hz),1.65 (q, 2H, J=8 Hz), 1.44-1.20 (m, 22H), 0.89 (t, 3H, J=6.8 Hz).

Preparation of Compound 5a

A solution of compound 8a (6.35 g, 13.6 mmol), compound 6a (10.75 g, 30mmol) and Pd(PPh₃)₄ (1.58 g, 1.36 mmol) were mixed in DMF (60 mL) andstirred at 90° C. for 4 hrs. The resultant suspension was diluted withH₂O (100 mL) and the solids were isolated by filtration. The solids weretaken up in a hexane/ethyl acetate mixture (v/v 3:1, 60 mL) and theslurry was stirred for 30 minutes at 60° C. The resultant suspension wascooled to room temperature and the solids were collected by filtration,and washed thoroughly with hexane (3×20 mL) to yield compound 5a asyellow solid (6.6 g, 69%). ¹H NMR (400 MHz, CDCl₃) δ 7.26 (s, 2H), 6.99(s, 2H), 6.70 (s, 2H), 2.81 (t, 4H, J=7.6 Hz), 1.70 (m, 4H, J=7.6 Hz),1.44-1.20 (m, 44H), 0.87 (t, 6H, J=7.6 Hz).

Preparation of Compound 4a

A solution of compound 5a (6.6 g, 9.46 mmol) in CHCl₃ (200 mL) wastreated with N-bromo-succinimide (3.7 g, 20.8 mmol) portion wise over 30minutes at 0° C. The resultant mixture was gradually warmed to roomtemperature and stirred for 3 hrs. H₂O (300 mL) was added to thereaction mixture and extracted with CH₂Cl₂ (3×60 mL). The combinedorganic layers were dried and concentrated to give a brown solid. Thesolid was taken up in a hexane/ethyl acetate mixture (v/v 3:1, 100 mL)and stirred for 30 minutes at 60° C. The resultant solids were collectedby filtration and washed thoroughly with hexane (3×10 mL) to yieldcompound 4a as yellow solid (6.3 g, 77%). ¹H NMR (400 MHz, CDCl₃) δ 7.60(s, 2H), 6.83 (s, 2H), 2.74 (t, 4H, J=7.6 Hz), 1.67 (m, 4H, J=7.6 Hz),1.44-1.20 (m, 44H), 0.87 (t, 6H, J=6.8 Hz).

Preparation of Compound 3a

Compound 4a (2.56 g, 3 mmol), trimethyl(2-tributylstannylethynyl)silane(3.50 g, 9 mmol) and Pd(PPh₃)₄ (350 mg, 0.3 mmol) were mixed in DMF (50mL) and stirred at 120° C. for 3 hrs. The reaction mixture was dilutedwith H₂O (150 mL) and extracted with CH₂Cl₂ (3×60 mL). The combinedorganic layers were dried and concentrated in vacuo to give a brown oil,which was purified by column chromatography on silica gel using 100%hexane to give compound 3a as yellow solid (2 g, 74%). ¹H NMR (400 MHz,CDCl₃) δ 7.81 (s, 2H), 6.90 (s, 2H), 2.76 (t, 4H, J=7.6 Hz), 1.63 (m,4H, J=7.6 Hz), 1.44-1.20 (m, 44H), 0.92 (t, 6H, J=7.2 Hz), 0.30 (s,18H).

Preparation of Compound 2a

A reaction mixture of compound 3a (1.90 g, 2.15 mmol) and K₂CO₃ (1.13 g,8.15 mmol) in MeOH/THF (v/v 1:1, 60 mL) mixture was stirred at roomtemperature for 20 hrs. The resultant suspension was diluted with THF(20 mL) and filtered. The residue was washed thoroughly with CH₂Cl₂ (20mL) and the filtrate was concentrated in vacuo. The resultant crudesolids were purified by column chromatography on silica gel using 100%hexane to yield compound 2a as yellow solid (0.8 g, 50%). ¹H NMR (400MHz, CDCl₃) δ 7.81 (s, 2H), 6.90 (s, 2H), 3.68 (s, 2H), 2.77 (t, 4H,J=7.6 Hz), 1.68 (m, 4H), 1.44-1.20 (m, 44H), 0.87 (t, 6H, J=7.2 Hz).

Preparation of Compound 1a

Compound 2a (100 mg, 0.134 mmol) and PtCl₂ (16 mg, 0.027 mmol) weremixed in toluene (20 mL) and heated at 60° C. for 20 hrs. The reactionmixture was cooled to room temperature and filtered. The filtrate wasconcentrated and purified by column chromatography on silica gel usinghexane/toluene (v/v 3:1) to yield compound 1a as yellow solid (8 mg,8%). ¹H NMR (400 MHz, CDCl₃) δ 7.81 (d, 2H, J=8.4 Hz), 7.76 (d, 2H,J=8.4 Hz), 2.99 (t, 4H, J=7.6 Hz), 1.81 (m, 4H, J=7.6 Hz), 1.45-1.15 (m,44H), 0.87 (t, 6H, J=6.8 Hz).

Example 2

Preparation of Compound 1 b

Preparation of Compound 12a

Commercially available LDA solution (2 M, 10 mL, 20.0 mmol) was dilutedin THF (75 mL) solution at 0° C. A solution of compound 7a (6 g, 16.7mmol) in THF (75 mL) was added drop wise to the dilute LDA solution at0° C. using a dropping funnel. The resultant mixture was graduallywarmed to room temperature and stirred for 3 hrs. The reaction mixturewas then cooled to −78° C. and transferred via cannula into a cooledsolution of I₂ in THF (150 mL) at −78° C. The reaction mixture wasallowed to stir at this temperature for 2 hrs. The reaction mixture wasquenched with water (150 mL) and extracted with Et₂O (2×150 mL). Thecombined organic layers were washed with Na₂S₂O₃, dried over MgSO₄ andconcentrated. The crude material was purified by column chromatographyon silica gel using 100% hexane to yield compound 12a as yellow oil (7g, 86%). ¹H NMR (400 MHz, CDCl₃) δ 6.60 (s, 1H), 2.75 (t, 2H, J=7.2 Hz),1.62 (m, 2H, J=7.2 Hz), 1.30-1.25 (m, 22H), 0.89 (t, 3H, J=7.2 Hz).

Preparation of Compound 11a

Compound 8a, prepared as described in example 1, (2.3 g, 4.93 mmol),compound 12a (6.7 g, 13.8 mmol) and Pd(PPh₃)₄ (0.6 g, 0.49 mmol) wereadded in a reaction vessel and evacuated 3 times with nitrogen. DMF (49mL) was then added and stirred at 70° C. for 22 h. The resultantsuspension was diluted with H₂O (100 mL) and the solids were isolated byfiltration. The solids were washed thoroughly with H₂O (5×50 mL) andhexane (20 mL) to yield compound 11a as orange solid (4 g, 95%). ¹H NMR(400 MHz, CDCl₃) δ 7.52 (s, 2H), 6.73 (s, 2H), 2.76 (t, 4H, J=7.6 Hz),1.67 (m, 4H, J=7.6 Hz), 1.36-1.26 (m, 44H), 0.88 (t, 6H, J=7.6 Hz).

Preparation of Compound 10a

Into a solution of compound 11a in 8 mL anhydrous THF at −78° C., 1.6 Mn-BuLi (0.55 mL, 0.88 mmol) was added dropwise within 15 minutes. Thesolution changed from greenish yellow to slurry orange solution. After 2hrs stirring at −78° C., DMF (0.1 mL, 1.2 mmol) in 2 mL anhydrous THFwas added. The reaction mixture was slowly allowed to warm up to roomtemperature and stirred overnight. The mixture was poured into 30 mLwater and then extracted with diethyl ether (3×20 mL). The organic layerwas washed with water (3×20 mL), dried over anhydrous MgSO₄, andconcentrated. The orange solid was purified by column chromatographyusing hexane/toluene (v/v 3:1) to give compound 10a as orangecrystalline solid (202 mg, 67%).

¹H NMR (400 MHz, CD₂Cl₂) δ 10.08 (s, 2H), 7.48 (s, 2H), 7.22 (s, 2H),2.82 (t, 4H, J=8 Hz), 1.71 (m, 4H, J=7.6 Hz), 1.40-1.27 (m, 44H), 0.88(t, 6H, J=6.8 Hz).

Preparation of Compound 9a

Into a slurry white solution of (methoxymethyl) triphenylphosphoniumchloride (1.061 g, 3.1 mmol) and 20 mL anhydrous THF at 0° C., cooled onice bath, anhydrous potassium tert-butoxide (321 mg, 2.86 mmol) wasadded, the reaction turned into orange solution immediately and followedby stirring for 1 h at 0° C. The compound 10a (377 mg, 0.5 mmol) wasadded, the reaction solution was warmed up to room temperature andstirred for 3 hrs. The mixture was washed with water (20 mL), extractedwith toluene (3×20 mL). The organic layer was collected, washed withwater, dried with anhydrous MgSO₄, and concentrated. The orange residuewas purified by column chromatography using hexane/toluene (v/v 9:1) togive compound 9a as orange solid (307 mg, 76%). ¹H NMR (400 MHz, CD₂Cl₂)δ 7.21 (s, 2H), 7.03 (d, 2H, J=13.2 Hz), 6.77 (s, 2H), 6.10 (d, 2H,J=13.2 Hz), 3.68 (s, 6H), 2.76 (t, 4H, J=8 Hz), 1.68 (m, 4H, J=7.6 Hz),1.39-1.27 (m, 44H), 0.88 (t, 6H, J=7.2 Hz).

Preparation of Compound 1b

Into a 50 mL Schlenk flask covered with aluminium foil, compound 9a (81mg, 0.1 mmol) was dissolved in 2 mL of anhydrous dichloromethane. Thesolution was cooled on ice. After the addition of 1 drop ofmethanesulfonic acid, the reaction solution was warmed up to roomtemperature and stirred overnight. The precipitates were filtered andwashed with methanol to yield a yellow solid. The crude compound 1b wasrecrystallized from hot hexane to yield compound 1b as yellow solid (45mg, 60%). ¹H NMR (400 MHz, CD₂Cl₂) δ 7.80 (d, 2H, J=8.4Hz), 7.74 (d, 2H,J=8.4Hz), 7.16 (s, 2H), 2.98 (t, 4H, J=7.6 Hz), 1.80 (q, 4H, J=7.6 Hz),1.45-1.21(m, 44H), 0.87 (t, 6H, J=7.2 Hz).

Example 3

Preparation of Bottom-Gate, Top-Contact Organic Field Effect Transistors(OFETs) Comprising Compound 1a, Respectively, 1b as SemiconductingMaterial

Thermally grown silicon dioxide (thickness: 200 nm) was used asdielectric layer. The gate electrode was formed by depositing highlydoped silicon on one side of the dielectric layer. The semiconductinglayer was formed by evaporation of compound 1a, respectively, by eitherevaporation or solution deposition (chlorobenzene, 1 mg/ml, drop castingat 70° C.) of compound 1b on the other side of the dielectric layer.Source/drain Au electrodes (thickness: 50 nm) were deposited through ashadow mask to give top-contact OFET devices. The channel width (W) wastypically 50 μm and channel length (L) is 1000 μm.

The design of the bottom-gate, top-contact organic field effecttransistor of example 3 is shown in FIG. 1.

Example 4

Measurement of the Transfer Curves and the Output Curves of theBottom-Gate, Top-Contact Organic Field Effect Transistors (OFETs)Comprising Compound 1a, Respectively, 1b

The drain current I_(d) [A] in relation to the gate-source voltage V_(g)[V] (top transfer curve) and the drain current I_(d) ^(1/2) [A^(1/2)] inrelation to the gate-source voltage V_(g) [V] (bottom transfer curve)for the bottom-gate top-contact organic field effect transistor ofexample 3 comprising compound 1b as semiconducting material at a drainvoltage V_(d) of −60 V was determined in air at room temperature using aKeithley 4200 machine. The results are shown in FIG. 2.

The drain current I_(d) [A] in relation to the drain voltage V_(d) [V](output curves) for the bottom-gate, top-contact organic field effecttransistor of example 3 comprising compound 1b as semiconductingmaterial at a gate-source voltage V_(g) of −60 V (first and top curve),−40 V (second curve), −20 V (third curve) and 0 V (fourth and bottomcurve) was determined in air at ambient temperature using a Keithley4200 machine. The results are shown in FIG. 3.

The drain current I_(d) [A] in relation to the gate-source voltage V_(g)[V] (top transfer curve) and the drain current I_(d) ^(1/2) [10⁻³A^(1/2)] in relation to the gate-source voltage V_(g) [V] (bottomtransfer curve) for the bottom-gate top-contact organic field effecttransistor of example 3 comprising compound 1a as semiconductingmaterial at a drain voltage V_(d) of −40 V was determined in air at roomtemperature using a Keithley 4200 machine. The results are shown in FIG.4.

The drain current I_(d) [μA] in relation to the drain voltage V_(d) [V](output curves) for the bottom-gate, top-contact organic field effecttransistor of example 3 comprising compound 1a as semiconductingmaterial at a gate-source voltage V_(g) of −60 V (first and top curve),−55 V (second curve), −50 V (third curve) and −45 V (fourth and bottomcurve) was determined in air at ambient temperature using a Keithley4200 machine. The results are shown in FIG. 5.

The compounds 1a and 1b show the typical behavior of a p-typesemiconducting material.

The charge-carrier mobility was extracted in the saturation regime fromthe slope of I_(d) ^(1/2) [μA^(1/2)] versus V_(g) [V]. The thresholdvoltage V_(th) [V] was obtained using the following equation:μ=2I _(d)/{(W/L)C _(μ)(V _(g) −V _(th))²}wherein Cμ is the capacitance of the dielectric layer.

The average values of the charge carrier mobility μ_(sat) [cm²/V s], theI_(ON)/I_(OFF) ratio and the threshold voltage V_(th) [V] for thebottom-gate, top-contact organic field effect transistor of example 3comprising compound 1a, respectively, 1b as semiconducting material aregiven in table 1.

TABLE 1 process of deposition of μ_(sat) V_(th) Compounds semiconductinglayer [cm²/V s] I_(on)/I_(off) [V] 1a Evaporation 0.90 3 * 10⁸ −47 1bSolution 8 * 10⁻³ 5 * 10³ −39 1b Evaporation 0.03 1 * 10⁵ −47

Example 5

Preparation of Compound 1a

Preparation of Compound 12a

A solution of 5a (7.8 g, 11.2 mmol), prepared as described in example 1,in CH₂Cl₂ (100 ml) was added drop wise to a mixture of POCl₃ and DMF inCH₂Cl₂ over 30 minutes at 0° C. The resultant mixture was graduallywarmed to room temperature and stirred in a 40° C. hot water bath for 2hours. The reaction mixture was diluted with CH₂Cl₂ and poured into ice(250 g) and stirred. KOAc (25 g) was added portion wise into the coldsolution and mixed thoroughly. The organic layer was separated andconcentrated to give crude product. The resultant solids were collectedby filtration and washed thoroughly with CH₂Cl₂ (3×20 mL) to yieldyellow solid (9.0 g, 98%).

¹H NMR (400 MHz, CDCl₃) δ 7.60 (s, 2H), 6.83 (s, 2H), 2.74 (t, 4H, J=7.6Hz), 1.67 (q, 4H, J=7.6 Hz), 1.44-1.20 (m, 44H), 0.87 (t, 6H, J=6.8 Hz).

Preparation of Compound 13a

12a (2.4 g, 3.0 mmol) in THF (90 mL) was added drop wise to a mixture of(methoxymethyl)triphenylphosphonium chloride (6.2 g, 18 mmol) andKO^(t)Bu (2.0 g, 18 mmol) in THF (60 ml) at −50° C. in a dryice-acetonitrile bath. The resultant mixture was left to stir in thecooling bath and slowly warmed to room temperature over 16 hrs. Thereaction mixture was diluted with diethyl ether (100 mL) and brine (100mL). The organic layer was separated and the aqueous layer furtherextracted with CH₂Cl₂ (3×50 mL). Combined organic layers wereconcentrated and purified by column chromatography on silica gel usinghexanes/toluene (v/v 1:1) to give yellow solid (1.1 g, 42%). ¹H NMR (400MHz, CDCl₃) δ 7.21 (s, 2H), 6.96 (d, 2H, J=12.8 Hz), 6.79 (s, 2H), 6.24(d, 2H, J=12.8 Hz), 3.69 (s, 2H), 2.77-2.70 (m, 4H), 1.62-1.75 (m, 4H),1.45-1.20 (m, 44H), 0.87 (t, 6H, J=6.8 Hz).

Preparation of Compound 1a

An isomeric mixture of 13a in CH₂Cl₂ (45 mL) was treated withmethanesulfonic acid (0.05 mL) drop wise at 0° C. in the dark. Theresultant mixture and stirred for 16 hrs at room temperature. Thereaction mixture was concentrated to dryness and the resultantprecipitate triturated with methylene chloride, then separated byfiltration. The residue was washed with H₂O and methanol. The crudeproduct was recrystallized from hot hexanes to give yellow solid (0.5 g,52%).

¹H NMR (400 MHz, CD₂Cl₂) δ 7.84 (d, 2H, J=8.4 Hz), 7.77 (d, 2H, J=8.4Hz), 7.27 (s, 2H), 2.98 (t, 4H, J=7.6 Hz), 1.75-1.85 (m, 4H), 1.40-1.20(m, 44H), 0.85 (t, 6H, J=6.8 Hz).

The invention claimed is:
 1. A compound of formula (1)

wherein o is 1, 2 or 3, p is 0, 1 or 2, n is 0, 1 or 2, m is 0, 1 or 2,A is a mono -or dicyclic ring system A, which contains at least S atom,wherein R¹⁰ is at each occurrence C₁₋₃₀-alkyl, wherein at least oneCH₂-group of C₁₋₃₀-alkyl, but not adjacent CH₂-groups, is optionallyreplaced with —O— or —S—, C₁₋₃₀-alkyl is optionally substituted with 1to 10 R¹⁰⁰ residues at each occurrence selected from the groupconsisting of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(a)), —N(R^(a))₂,—NH—C(O)—(R^(a)), —N(R^(a))—C(O)—(R^(a)), —N[C(O)—(R^(a))]₂,—C(O)—R^(a), —C(O)—OR^(a), —C(O)NH₂, —CO(O)NH—R^(a), —C(O)N(R^(a))₂,—O—R^(a), —O—C(O)—R^(a), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, and wherein R^(a) is at eachoccurrence selected from the group consisting of C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyland C₂₋₂₀-alkynyl are optionally substituted with 1 to 5 residues ateach occurrence selected from the group consisting of halogen, CN, —NO₂,—OH, —NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 memberedheterocyclic ring system; R³ and R¹¹ are independently from each otherat each occurrence selected from the group consisting of halogen, —CN,—NO₂, C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, C₄₋₈-cycloalkyl,C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ring system, wherein atleast one CH₂-group of CH₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and C₂₋₃₀-alkynyl,but not adjacent CH₂-groups, is optionally replaced with —O— or —S—, andC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl and C₂₋₃₀-alkynyl are optionally substitutedwith 1 to 10 R¹⁰¹ residues independently selected from the groupconsisting of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,—NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,—C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b), —C(O)N(R^(b))₂,—O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, and wherein R^(b) is at eachoccurrence selected from the group consisting of C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl orC₂₋₂₀-alkynyl are optionally substituted with 1 to 5 residues at eachoccurrence selected from the group consisting of halogen, CN, —NO₂, —OH,—NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclicring system, and C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 memberedheterocyclic ring system are optionally substituted with 1 to 5 residuesindependently selected from the group consisting of halogen, CN, —NO₂,—OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.
 2. Thecompound of claim 1, wherein A is


3. The compound of claim 1, wherein R¹⁰ is at each occurrenceC₈₋₂₀-alkyl.
 4. The compound of claim 1, wherein R³ and R¹¹ areindependently from each other at each occurrence selected from the groupconsisting of halogen, —CN, C₁₋₃₀-alkyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl,and a 5 to 14 membered heterocyclic ring system, wherein at least oneCH₂-group of C₁₋₃₀-alkyl, but not adjacent CH₂-groups, is optionallyreplaced with —O— or —S—, and C₁₋₃₀-alkyl is optionally substituted with1 to 10 R¹⁰¹ residues independently selected from the group consistingof halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)), —N(R^(b))₂,—NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b))]₂,—C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b), —C(O)N(R^(b))₂,—O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, and wherein wherein R^(b) is at eachoccurrence selected from the group consisting of C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl orC₂₋₂₀-alkynyl is optionally substituted with 1 to 5 residues at eachoccurrence selected from the group consisting of halogen, CN, —NO₂, —OH,—NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclicring system, and C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 memberedheterocyclic ring system are optionally substituted with 1 to 5 residuesindependently selected from the group consisting of halogen, CN, —NO₂,—OH, —NH₂, C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.
 5. Thecompound of claim 1, wherein R³ and R¹¹ are independently from eachother at each occurrence selected from the group consisting ofC₁₋₃₀-alkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ringsystem, wherein at least one CH₂-group of C₁₋₃₀-alkyl, but not adjacentCH₂-groups, is optionally replaced with —O— or —S—, and C₁₋₃₀-alkyl isoptionally substituted with 1 to 10 R¹⁰¹ residues independently selectedfrom the group consisting of halogen, —CN, —NO₂, —OH, —NH₂, —NH(R^(b)),—N(R^(b))₂, —NH—C(O)—(R^(b)), —N(R^(b))—C(O)—(R^(b)), —N[C(O)—(R^(b)])₂, —C(O)—R^(b), —C(O)—OR^(b), —C(O)NH₂, —CO(O)NH—R^(b), —C(O)N(R^(b))₂,—O—R^(b), —O—C(O)—R^(b), C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, and wherein wherein R^(b) is at eachoccurrence selected from the group consisting of C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14membered heterocyclic ring system, wherein C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl orC₂₋₂₀-alkynyl is optionally substituted with 1 to 5 residues at eachoccurrence selected from the group consisting of halogen, CN, —NO₂, —OH,—NH₂, C₄₋₈-cycloalkyl, C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclicring system, and C₆₋₁₄-aryl, and a 5 to 14 membered heterocyclic ringsystem are optionally substituted with 1 to 5 residues independentlyselected from the group consisting of halogen, CN, —NO₂, —OH, —NH₂,C₁₋₁₀-alkyl, C₂₋₁₀-alkenyl, and C₂₋₁₀-alkynyl.
 6. The compound of claim1, wherein o is
 1. 7. The compound of claim 1, wherein p, n and m are 0.8. The compound of claim 1, wherein the compound of formula (1) isselected from the group consisting of formulae (1′a) and (1′b)

wherein R¹⁰ is C₈₋₂₀-alkyl.
 9. An electronic device comprising thecompound according to claim
 1. 10. The electronic device of claim 9,wherein the electronic device is an organic field effect transistor(OFET).
 11. A method comprising incorporating the compound according toclaim 1 as a semiconducting material.